Halonitromethyl cycloalkanes

ABSTRACT

COMPOUNDS CORRESPONDING TO THE FORMULA   X-CH&lt;(-(CH2)N-CH(-C(-X)(-NO2)-CL)-)   WHEREIN EACH X INDEPENDENTLY REPRESENTS CHLORO OR BROMO AND N REPRESENTS AN INTERGER OF 3 TO 4 PREPARED. THE COMPOUNDS HAVE BEEN FOUND TO BE ACTIVE INSECTICIDES, HERBICIDES, BACTERICIDES, FUGICIDES AND NEMATOCIDES.

P 3,754,042 Ice Patented Aug. 21, 197

United States Patent light source, i.e. source of ultraviolet light. The reaction 3,754,042 can be characterized as follows: HALONITROMETHYL CYCLOALKANES X Wilson F. Gum, Jr., and David A. Nelson, Midland,

Mich., assignors to The Dow Chemical Company, 5 X Midland, Mich. No Drawing. Filed Sept. 15, 1972, Ser. No. 289,322 H 1 Int. Cl. C07c 79/08 US. Cl. 260-644 8 Claims or I C N I hv or ABSTRACT OF THE DISCLOSURE 10 or x Compounds corresponding to the formula 2 01 m H x x-o-Nm H H In carrying out this reaction, a solution is prepared g containing the cycloalkene and the halopicrin in a solvent (reaction medium) such as, for example, benzene, n-hexwherein each X independently represents chloro bromo ane, toluene or heptane. The reaction solution is placed and n; represents an integer of 3 or 4 are prepared. The in a photochemical reaction vessel equipped with an compounds have been found to be active insecticides, ultraviolet light source, a cooling coil, a thermocouple, a herbicides, bacteriocides, fungicides and nematocides. nitrogen bubbler and agitation means.

Since the reaction consumes the reactants in amounts Prior art representing equimolecular proportions, these amounts for the most part can be employed. It has been found Various halonitromethylalkanes have been prepared by however that an increase in yield can be obtained by the reaction of halonitromethanes or ethanes with olefins employing an excess of the halopicrin. Therefore, it is as shown by Baskakov et al. Zhur. Obsch. Khim 29 1203 preferred to employ from 1 mole of the halopicrin per (1959). However, no stable halonitromethylcycloalkanes mole of the cycloalkene up to 3 moles or more of the have been produced. The halonitromethanes themselves 30 halopicrin per mole of the cycloalkene.

and their preparation have been taught in US. Pat. The reaction is initiated by first sparging the reaction 3,159,686. mixture with nitrogen for a period of from about 10 to SUMMARY OF THE INVENTION about 30 minutes and thereafter irradiating the mixture for a period of from about 8 to about 25 hours while This invention is directed to halomtromethylcyclothe temperature is maintained between about 25 and alkane compounds corresponding to the formula about 45 C. Upon completion of the reaction, the solvent is removed by evaporation under reduced pressure and i the crude reaction product purified by multiple distillax X- --N0i tion, if desired. H H Alternatively, the compounds can be prepared in higher fi yields by reacting the halopicrin and cycloalkene together in the presence of a redox-transfer catalyst such as, for In this and succeeding formulae, each X independently p l pf Chloride in q y f e hYdFOCPIOI'ide represents chloro or bromo and n represents an integer 4 and eeetomtllleer eupfle ehlol'lde 1H dlethylamme- III f 3 or 4. carrying out this reaction, the reactants are contacted The novel compounds of this invention are usually together in The Presence of the catalyst and heated at liquids having very slight solubility in water and good reflux temperature, b ut to 60 C. for from about solubility in conventional organic solvents such as ace- 3 to about 20 l Thereafter, the r actlon mixture 15 tone, benzene, dichloromethane, carbon tetrachloride, 5 f Washed Wlth dllllte P hydl'eehlefle ethanol and isopropanol, These novel compounds have acid, followed by water washing and thereafter dried at utility in a wide variety of agricultural applications. Thus, Ilslng a dessleant Such as anhydrous Potassium some of the compounds are useful in agronomical prace or magneslum Sulfate The Product can e furthe tices for the selective control of various weeds. Many are Pllflfied if deslred y distillationalso useful as fungicides, bacteriocides, nematocides and DESCRIPTION OF SOME PREFERRED msectcldes- EMBODIMENTS Representative novel compounds coming within the scope f the present invention include the following: The following examples serve to illustrate the practice of the present invention but are not intended to be limital'bromo'z'(dichloronitmmethyl)cyclopentane; tions on the overall scope of the invention.

1-chloro-2-(dichloronitromethyl)cyclopentane; 1-bromo-2-(bromochloronitromethyl)cyclopentane; Example 1'lbromoz(dlchloromtwmethyl) 1-chloro-2- (bromochloronitromethyl) cyclopentane; cyclohexane l-bromo-Z-(dichloronitromethyl)cyclohexane; l-chloro-Z- (dichloronitromethyl) cyclohexane; 1-bromo-2-(bromochloronitromethyl)cyclohexane; and C0111: 1-chloro-2-('bromochloronitromethyl)cyclohexane. H

The halonitromethylcycloalkane compounds of the present invention can be prepared by reacting a halopicrin A solution was prepared containing 8.2 grams (0.1

(trichloronitromethane, dibromochloronitromethane or mole) of cyclohexene and 62.7 grams (0.3 mole) of dichlorobromonitromethane) with a cycloalkene (cyclobromodichloronitromethane (CCl B'rNO in 50 millipentene or cyclohexene) in the presence of an irradiation liters of benzene. The solution was sparged with nitrogen for minutes and thereafter irradiated with a sunlamp for 25 hours while the temperature was maintained at between 40 and 45 C. The reaction mixture was distilled to remove excess bromodichloronitromethane and redistilled obtaining a fraction boiling at 90-100 C. at 0.2 millimeter of mercury (mm.). This fraction was further distilled to recover the l-bromo 2- (dichloronitromethyl)cyclohexane product. This product upon analysis was found to have carbon, hydrogen, nitrogen, chlorine and bromine contents of 29.0, 3.35, 4.81, 23.1 and 27.9 percent, respectively, as compared with the theoretical contents of 28.9, 3.44, 4.82, 24.4 and 27.4 percent, respectively, calculated for the above named product. The product boils at 9092 C. at 0.2 mm. and has a refractive index of n 25/D=1.5369. The structure was confirmed by nuclear magnetic resonance (N.M.R.) spectrum and infra-red analysis (IR).

The same product was obtained employing the same reactant in equimolar amounts.

In an analogous manner employing generally the method of Example 1 and the appropriate halopicrin and cycloalkene, the following compounds are prepared:

l-bromo 2 (bromochloronitromethyl)cyclohexane, having a boiling point of 110115 C. at 0.2 mm. and a refractive index of n 25/D=1.5572 and l-bromo-Z (dichloronitromethyl)cyclopentane, having a boiling point of 89 -91 C. at 0.5 mm. and a refractive index of n 25/D=1.5230.

Example II.1-bromo-2- (bromochloronitromethane) cyclopentane 0 01B rN 0,

To a mixture of 17 grams (0.25 mole) of cyclopentene and 63.3 grams (0.25 mole) of dibromochloronitromethane was added a solution comprising 0.55 grams (0.005 mole) of diethylamine hydrochloride and 0.45 gram (0.02 mole) of cupric chloride in milliliters of acetonitrile. The mixture was heated at reflux for 2 hours and thereafter cooled. The reaction mixture was Washed twice with 200 milliliter portions of 2 molar hydrochloric acid followed by two water washes (300 milliliters each). The washed reaction medium was dried over anhydrous potassium sulfate under refrigeration at 0 C. and the unreacted dibromochloronitromethane removed by distillation at 40 C. and 1.0 mm. The 1-br0mo-2-(bromochloronitromethyl)cyclopentane product was recovered by an additional distillation step and boils at 7980 C. at 0.1 mm. and has a refractive index of n 25/D=1.5471. The structure of the compound was confirmed by N.M.R. and IR.

In an analogous manner employing generally the method-of Example II and the appropriate halopicrin and cycloalkene, the following compounds are prepared.

l-chloro 2 (bromochloronitromethyl)cyclohexane having a molecular weight of 290.91;

1-chloro-2 (dichloronitromethyl)cyclopentane having a molecular weight of 232.44;

1-chloro-2-(dichloronitromethyl)cyclohexane having a boiling point of 102-104 C. at 0.8 mm. and

l-chloro 2 (bromochloronitromethyl)cyclopentane having a molecular weight of 276.90.

The compounds of the present invention are employed as toxicants in herbicides, insecticides, bacteriocides, nematocides, and fungicides. For such uses, the compounds can be employed in an unmodified form or dispersed on a finely divided solid and employed as dusts. Such mixtures can also be dispersed in water with or without the aid of a surface active agent and the resulting aqueous suspensions employed as sprays. In other procedures, the products can be employed as active constituents in solvent solutions, oil-in-water or water-in-oil emulsions or aqueous dispersions. The augmented compositions are adapted to be formulated as concentrates and subsequently diluted with additional liquid or solid adjuvants to produce the ultimate treating compositions. Good results are obtained when employing compositions containing the toxicant in concentrations usually from about 0.1 to about 10,000 parts or more by weight of one or more of the compounds per million parts of such compositions.

In a representative operation, 1-bromo-2-(dichloronitromethyl)cyclopentane when employed as the sole toxicant in an aqueous dispersion at a concentration of 500 parts per million parts by weight was found to give substantial kill and control of southern armyworm larvae.

-In additional operations, 1-bromo-2-(bromochloronitromethyl)cyclopentane when employed as the sole toxicant in an aqueous dispersion at a concentration of about 1 part per million parts by weight was found to give percent kill and control of yellow fever mosquito larvae; and at a concentration of 500 parts per million parts by weight was found to give 100 percent kill and control of codling moths.

In another representative operation, each of the compounds l-chloro 2 (dichloronitromethyl)cyclohexane, 1 bromo 2 (bromochloronitromethyl)cyclopcntane, 1 bromo 2 (dichloronitromethyl)cyclopentane, 1- bromo 2 (bromochloronitromethyl)cyclohexane and l bromo 2 (dichloronitromethyl)cyclohexane when employed as the sole toxicant in a nutrient agar at a concentration of about 500 parts by weight per million parts of agar were found to give 100 percent kill and control of the organisms Candida albicans, Trichophyton mcnla grophytes, Bacillus subtilis, Candida pelliculosa, Pullularia pullulans, Mycobacterium pheli and Rhizopus nigricans.

In additional operations employing the same toxicant concentrations in nutrient agar, each of the compounds 1- bromo-2-(bromochloronitromethyl)cyclohexane and 1- bromo-2-(dichloronitromethyl)cyclohexane were found to give 100 percent kill and control of the organisms Staphylococcus aureus and Salmonella typhosa;

In herbicidal use operations, each of the compounds 1- bromo 2 (bromochloronitromethyl)cyclohexane, 1- bromo-Z-(dichloronitromethyl)cyclohexane and l-bromo- 2- (bromochloronitromethyl)cyclopentane when applied as the sole toxicant in an aqueous dispersion at a dosage rate of 4,000 parts by weight per million parts of the ultimate dispersion were found to give 100 percent kill and control of pigweed plants.

In additional operations, each of the compounds 1- bromo-Z-(bromochloronitromethyl)cyclopentane and 1- chloro-Z-(dichloronitromethyl)cyclohexane when applied post-emergent to barnyard grass, as the sole toxicant in an aqueous dispersion at a dosage rate equivalent to 20 pounds per acre were found to give excellent kill and control of the plants. In an additional operation l-chloro- 2-(dichloronitromethyl)cyclohexane was found to give 100 percent kill and control of yellow foxtail when applied at the same dosage as above.

In other operations, each of the compounds l-bromo-2- (dichloronitromethyl)cyclohexane and 1 bromo 2- (bromochloronitromethyl)cyclohexane, when applied post-emergent to pigweed, as the sole toxicant in an aqueous dispersion at a dosage rate equivalent to 10 pounds per acre were found to give 100 percent kill and control of the plants.

In another representative operation, each of the compounds l-bromo-Z-(dichloronitromethyl)cyclohexane and 1-bromo-2-(dichloronitromethyl)cyclopentane were found to give 100 percent kill and control of the Rootknot nematode when soil containing the nematode was treated with one of the compounds as the sole toxicant in the amount of 3 parts by weight per million parts of the soil.

When applied at a dosage level of from about 500 4. The compound of claim 2 which is 1-br0rno-2-(dito about 10,000 parts per million, each of the compounds chloronitromethyl)cyclopentane. of the present invention, the utility of which is not spe- 5. The compound of claim 1 wherein n represents the cifically recited hereinabove, has the ability to kill, inhibit integer 4. or otherwise control one or more of the above said or 5 6. The compound of claim 5 which is 1-chloro-2-(diother fungal, bacterial, insect, nematode, or weed pests. chloronitromethyl)cyclohexane.

What is claimed is: 7. The compound of claim 5 which is 1-bromo-2- 1. A compound corresponding to the formula (bromochloronitromethyl)cyclopentane.

8. The compound of claim 5 which is 1-br0mo-2-(di- C1 10 chloronitromethyl)cyclohexane. X X--t!J--NO: H H References Cited (0 2) UNITED STATES PATENTS 3,488,396 1/1970 Frankelet a1 260-644 wherein each X independently represents chloro or bromo 3,646,228 2/1972 Frankel et a1. 260--644 and n represents an integer of 3 or 4.

2. The compound of claim 1 wherein n represents the integer 3.

3. The compound of claim 2 which is 1-bron1o-2- 20 (bromochloronitromethyl)cyclopentane. 204162 R; 260-999; 424349 LELAND A. SEBASTIAN, Primary Examiner 53 3 UNITED STATES PATENT OFFICE CEB'ETIFICATE ()F CORRECTEON Patent; No. 3.754.042 Dated' August 21, 1973 Invenmfls) mihnn F. Gum. Jr. and David A. Nelson It is certified that error appears in the above-identified patent 4 and that said'Letters Patent are hereby corrected as shown below:

Claim 7, line 2 delete "cyclopentane" and substitute --cycl ohexane.

Signed and sealed this 18th day of December 1973.

(SEAL) Attest:

EDWARD M. FLETCHER, JR; RENE D. TEGTMEYER Attesting Officer Acting Commissioner of Patents 57 UNITED STATES PATENT OFFICE (IER'EHFICATE ()F CORRECTION Patent No. 3.754.042 Dated August 21, 1973 I vent m 'lqnn F. Gum. Jr. and David A. Nelson It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

' Claim 7, line 2, delete "cyclopentane" and substitute --cyclohexane-.

Signed and sealed this 18th day of December 1973.

(SEAL) Attest:

RENE D. TEG'I'MEYER Acting Commissioner of Patents EDWARD M. FLETCHER, JR. Attesting Officer 

